WO2017052323A1 - Phthalonitrile compound - Google Patents

Abstract

The present application can provide a phthalonitrile compound and a use thereof. The present application can provide a phthalonitrile compound capable of forming a phthalonitrile resin by self-curing or of serving as a curing agent after being mixed with another phthalonitrile compound, and a use of the phthalonitrile compound. The phthalonitrile compound can form a phthalonitrile resin by rapid self-curing even at a low temperature and does not create any defects resulting from the use of a conventional curing agent. Also, the phthalonitrile compound can be applied as a curing agent after being mixed with another compound, in which case, even if the content of the compound applied as a curing agent increases, the total content of the phthalonitrile resin obtained does not decrease, and thus a resin exhibiting an excellent degree of cure can be provided.

Description

Phthalonitrile compounds

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0135856 filed on September 24, 2015, and all the contents disclosed in the literature of those Korean patent applications are incorporated as part of this specification.

The present application is directed to phthalonitrile compounds, phthalonitrile resins, polymerizable compositions, prepolymers, composites, precursors thereof and methods of preparation and uses.

The phthalonitrile compound can be applied to various applications. For example, the phthalonitrile compound can be used as a raw material of the so-called phthalonitrile resin. For example, a composite formed by impregnating a phthalonitrile resin into a filler such as glass fiber or carbon fiber may be used as a material for automobiles, airplanes, ships, and the like. The manufacturing process of the composite may include, for example, a process of curing after mixing a prepolymer and a filler formed by a mixture of a phthalonitrile and a curing agent or a reaction of the mixture (for example, Patent Document 1 Reference).

As another use of a phthalonitrile compound, use as a precursor of a phthalocyanine pigment is mentioned. For example, the phthalonitrile compound may be applied as a pigment in combination with a metal.

The phthalonitrile compound may also be applied as a precursor of fluorescent brighteners or photographic sensitizers or precursors of acid anhydrides. For example, the phthalonitrile compound may be converted into an acid anhydride through an appropriate oxidation process and dehydration process, and the acid anhydride may be used as a precursor such as polyamic acid or polyimide.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Korean Registered Patent No. 0558158

The present application can provide novel phthalonitrile compounds and their uses. Examples of the use include phthalonitrile resins, polymerizable compositions or prepolymers for producing the same, composites, precursors of the complexes, and the like, or precursors or raw materials of pigments, fluorescent brighteners, photography sensitizers or acid anhydrides.

The present application is directed to phthalonitrile compounds. The compound may be represented by Formula 1 below.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently an aromatic divalent radical substituted with at least one amino group or hydroxy group, and L, L ₁ and L ₂ are each independently an alkylene group, an alkylidene group, an oxygen atom, sulfur Atom or —S (═O) ₂ —, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, wherein at least two of R ₁ to R ₅ are cyano groups, and R At least two of ₆ to R ₁₀ are cyano groups.

In the above Ar ₁ and Ar ₂ may be the same or different from each other, L, L ₁ and L ₂ may be the same or different from each other.

In the present application, the term aromatic divalent radical may refer to benzene, a compound containing benzene, or a divalent residue derived from any one of the above, unless otherwise specified. As the compound containing benzene in the above, it may mean a compound having a structure in which two or more benzene rings are condensed while sharing two carbon atoms, or connected by an appropriate linker. Aromatic divalent radicals may include, for example, 6 to 25, 6 to 20, 6 to 15 or 6 to 12 carbon atoms. Ar 1 and Ar 2, which are aromatic divalent radicals in Formula 1, may be substituted with at least one, one to five, one to four, one to three, or one to two amino or hydroxy groups, and It may be substituted with an amino group. The aromatic divalent radical may optionally be substituted by one or more substituents in addition to the amino group or the hydroxyl group.

In one example, the aromatic divalent radical may be a radical derived from an aromatic compound of any one of Formulas 2 to 4 below.

[Formula 2]

Are each in the formula (2) R ₁ to R ₆ independently selected from hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or ahminogiyi be, R ₁ to R _6, at least two of which form a radical, and R ₁ to R ₆ at least one of Dogs are hydroxy or amino groups.

[Formula 3]

Respectively in Formula (3) R ₁ to R ₈ independently selected from hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or ahminogiyi be, R ₁ to R at least two of the ₈ form a radical, and R ₁ to R _8, at least one of Dogs are hydroxy or amino groups.

[Formula 4]

In Formula 4, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, at least two of R ₁ to R ₁₀ form a radical, and L is an alkylene group or an alkyl group. It is a den group, an oxygen atom, or a sulfur atom, and at least 1 of R <_1> -R <_10> is a hydroxyl group or an amino group.

R ₁ to R ₆ of Formula 2, R ₁ to R ₈ of Formula 3 or R ₁ to R ₁₀ of Formula 4 each independently represent a hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, each of the two The above forms a radical. Forming a radical in the above may mean that the site is connected to other elements of the formula (1). For example, in the case of Ar ₁ in formula (1), share any one portion of the area which forms the radicals form a covalent bond is directly connected to L ₁ in the formula (1), and the other part is directly connected to the L of formula (I) A bond can be formed. In the case of Ar ₂ in Formula 1, any one of the sites forming the radical is directly connected to L ₂ of Formula 1 to form a covalent bond, and the other site is directly linked to L of Formula 1 to form a covalent bond. Can be. At least one, one to five, one to four, one to three or one to two of each of the above substituents which do not form a radical is an amino group or a hydroxyl group, and the remaining substituents are hydrogen, an alkyl group or An alkoxy group; It may be hydrogen or an alkyl group. In one example, in Formula 2, R ₁ and R ₄ or R ₁ and R ₃ may form the radical. In this case, one to three or one to two of the substituents which do not form a radical are an amino group or a hydroxyl group, and the other substituents are each independently hydrogen, an alkyl group, an alkoxy group or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In addition, in Formula 3, any one of R ₁ , R ₆ , R _7, and R ₈ and any one of R ₂ , R ₃ , R _4, and R ₅ may form the radical. In this case, one to five, one to four, one to three, or one to two of the substituents which do not form a radical are amino or hydroxy groups, and the other substituents are each independently hydrogen, an alkyl group, An alkoxy group or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In addition, in Formula 4, any one of R ₁ to R ₅ and any one of R ₆ to R ₁₀ may form the radical. In this case, one to five, one to four, one to three, or one to two of the substituents which do not form a radical are amino or hydroxy groups, and the other substituents are each independently hydrogen, an alkyl group, An alkoxy group or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group. In Formula 4, L may be an alkylene group, an alkylidene group, an oxygen atom or a sulfur atom, and in another example, may be an alkylene group, an alkylidene group or an oxygen atom, or an oxygen atom.

As a general example of Ar ₁ or Ar ₂ in Formula 1, the aromatic divalent radical of Formula 2 may be exemplified. In this case, the substituent at the meta position or the para position may be a hydroxy group or an amino group based on the substituent forming a covalent bond with L in Formula 1 in R ₁ to R ₆ of Formula 2.

In the present application, the term alkyl group may be an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkyl group may be linear, branched or cyclic and may be substituted by one or more substituents if necessary.

The term alkoxy group in the present application may be an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, unless otherwise specified. The alkoxy group may be linear, branched or cyclic and may be substituted by one or more substituents if necessary.

In the present application, the term aryl group may refer to benzene, a compound containing a benzene structure, or a monovalent moiety derived from any one of the above-mentioned derivatives unless otherwise specified. Aryl groups may include, for example, 6-25, 6-20, 6-15, or 6-12 carbon atoms. Specific examples of the aryl group may include, but are not limited to, a phenyl group, benzyl group, biphenyl group or naphthalenyl group. In addition, the scope of the aryl group in the present application may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group.

The term alkylene group or alkylidene group in the present application means an alkylene group or alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, unless otherwise specified. can do. The alkylene group or alkylidene group may be linear, branched or cyclic. In addition, the alkylene group or alkylidene group may be optionally substituted with one or more substituents.

In the present application, as the substituent which may be optionally substituted with the alkyl group, alkoxy group, aryl group, aromatic divalent radical, alkylene group or alkylidene group, halogen, glycidyl group, epoxyalkyl group, glyci such as chlorine or fluorine Epoxy groups, such as a doxyalkyl group or an alicyclic epoxy group, acryloyl group, methacryloyl group, an isocyanate group, a thiol group, an alkyl group, an alkoxy group, or an aryl group etc. can be illustrated, but it is not limited to these.

In Formula 1, L, L1, and L2 may be a single bond, an alkylene group, an alkylidene group, an oxygen atom, a sulfur atom, or —S (═O) ₂ —.

In one example, L in Formula 1 may be a single bond, an alkylene group, or an alkylidene group, or may be -S (= 0) _2- . The alkylene group or alkylidene group may be substituted with at least one halogen atom or haloalkyl group, that is, an alkyl group substituted with a halogen atom, if necessary, and optionally substituted with another substituent in addition to the halogen atom. have. Meanwhile, the term single bond refers to a case where no separate atom exists at a corresponding site. For example, when L is a single bond, a structure in which Ar 1 and Ar 2 are directly connected may be derived.

In Formula 1, L ₁ and L ₂ may be an alkylene group, an alkylidene group, or an oxygen atom, and in one example, may be an oxygen atom.

In Formula 1, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, at least two of R ₁ to R ₅ are cyano groups, and at least two of R ₆ to R ₁₀ It is a cyano group. In another embodiment, R ₁ to R ₁₀ that are not cyano groups are each independently hydrogen, an alkyl group, or an alkoxy group; Or hydrogen or an alkyl group. In one example, in Formula 1, any two of R ₂ to R ₄ and any two of R ₇ to R ₉ are cyano groups, and the remaining substituents are each independently hydrogen, an alkyl group, an alkoxy group, or an aryl group; Hydrogen, alkyl or alkoxy groups; Or hydrogen or an alkyl group.

The compound of formula 1 can be effectively used in various applications in which so-called phthalonitrile compounds are known to be applicable. For example, the phthalonitrile compound can be effectively used as a raw material or precursor capable of producing a so-called phthalonitrile resin. The compound exhibits a low melting temperature, is excellent in reactivity with the curing agent, and exhibits a wide process window, so that it can be effectively applied to the application. The compound may be applied to precursors or raw materials of dyes such as phthalocyanine pigments, fluorescent brighteners, photographic sensitizers or acid anhydrides, and the like, in addition to the above uses.

The compound of formula 1 can be synthesized according to the synthesis method of known organic compounds. For example, the compound of Formula 1 may be synthesized by reacting an aromatic compound having an phenolic hydroxy group with an aromatic compound substituted with an amino group or a hydroxy group and an aromatic compound having at least two cyano groups (ex. Nitro displacement method). Can be. In the field of organic chemistry, the aromatic compounds capable of forming the structure of the compound of Formula 1 are known, and all of these compounds may be applied to the preparation of the compound in consideration of the desired structure.

The present application also relates to the use of such compounds. As the use of the compound, as described above, phthalonitrile resin, phthalocyanine dye, fluorescent brightener, photography sensitizer or raw material or precursor of an acid anhydride may be exemplified.

As an example of the use, for example, the present application may be for a phthalonitrile resin. The phthalonitrile resin may include a polymer unit derived from the compound of Formula 1. In the present application, the term “polymerized unit derived from a compound” may refer to a skeleton of a polymer formed by polymerization or curing of the compound.

In the phthalonitrile resin, the polymerized unit of the compound of formula 1 is a polymerized unit formed by reaction of the compound with a curing agent, reaction between the compound of formula 1, or reaction of the compound of formula 1 with another phthalonitrile compound, and the like. Can be.

The compound of Formula 1 may include an amino group or a hydroxyl group which reacts with a cyano group by itself, and thus may form a polymerized unit without a separate curing agent. Therefore, the phthalonitrile resin can be formed only with the compound of Formula 1, and if necessary, the compound of Formula 1 can be used as a curing agent of another phthalonitrile monomer or a composition including the same. In this case, since the compound of Formula 1 itself participates in the reaction and becomes a constituent of the phthalonitrile resin, it is possible to increase the curing rate and the curing density, and the content of the compound of Formula 1 that acts as a curing agent Even if it becomes high, the fall of a physical property does not occur.

In the case of using only the compound of Formula 1 or applying phthalonitrile other than the compound of Formula 1 together with the compound of Formula 1 to form a phthalonitrile resin, a curing agent is not necessary as described above. You may mix and use other suitable hardening | curing agent.

The phthalonitrile resin may further include a polymerization unit of another phthalonitrile compound in addition to the polymerization unit of the compound of the formula (1). In this case, the kind of phthalonitrile compound that can be selected and used is not particularly limited, and known compounds known to be useful for the formation of phthalonitrile resins and the control of their physical properties can be applied. Examples of such compounds include U.S. Patent 4,408,035, U.S. Patent 5,003,039, U.S. Patent 5,003,078, U.S. Patent 5,004,801, U.S. Patent 5,132,396, U.S. Patent 5,139,054, U.S. Patent 5,208,318, U.S. Patent Compounds known from US Pat. No. 5,237,045, US Pat. No. 5,292,854 or US Pat. No. 5,350,828 may be exemplified, but are not limited thereto.

As described above, a curing agent may be used together with the compound of Formula 1 when necessary, and the type of curing agent is not particularly limited as long as it is usually used for forming phthalonitrile resin. Such hardeners are known in various documents, including the US patents described above.

In one example, an amine compound or a hydroxy compound such as an aromatic amine compound may be used as a curing agent. In the present application, a hydroxy compound may mean a compound including at least one or two hydroxy groups in a molecule.

The present application also relates to polymerizable compositions. The polymerizable composition may include the compound of Formula 1 above. The polymerizable composition may form a so-called phthalonitrile resin, and basically includes the compound of Formula 1, and may further include or may not include a curing agent. That is, as described above, the compound of Formula 1 may be cured by itself, and thus the polymerizable composition may not include an amine compound or a hydroxy compound that acts as a curing agent. That is, the polymerizable composition may not include a compound having an amine group or a hydroxyl group in addition to the compound of Formula 1.

If necessary, an appropriate curing agent may be included, and as the curing agent included in the polymerizable composition, for example, a curing agent as described above may be used. In the case where a curing agent is included, the proportion of the curing agent in the polymerizable composition is not particularly limited. For example, the ratio may be adjusted to ensure the desired curability in consideration of the ratio or type of the curable component such as the compound of Formula 1 included in the composition. For example, the curing agent may be included in about 0.02 mol to 2 mol or from 0.02 mol to 1.5 mol per mol of the compound of Formula 1 included in the polymerizable composition. However, the ratio is only an example of the present application. Usually, the ratio of the curing agent in the polymerizable composition is high, but the process window is narrow, and when the ratio of the curing agent is low, the curing property tends to be insufficient, so in view of this point, an appropriate ratio of curing agent can be selected. have.

In another example, the polymerizable composition may include another phthalonitrile compound other than the compound of Formula 1 above. As described above, the compound of Chemical Formula 1 may act as a curing agent. In this case, even when increasing the content of the compound of Formula 1, which acts as a curing agent, the content of the phthalonitrile resin does not decrease, and a high degree of curing resin can be obtained. When the compound of formula 1 is included in the polymerizable composition together with another phthalonitrile compound as a curing agent, the ratio is not particularly limited, and may be included, for example, in the range of 2 mol% to 95 mol% in the total composition. Can be.

The polymerizable composition comprising the compound of formula 1 can be quickly and easily cured even at low temperatures, for example up to about 350 ° C., and can exhibit low melting temperatures. In addition, as described above, when the compound of Formula 1 is included as a curing agent, even when the ratio is excessive, the compound of Formula 1 participates in the reaction, so that the components of the final product (phthalonitrile resin, etc.) Therefore, the fall of physical properties can be prevented.

The polymerizable composition may further include various additives including other phthalonitrile compounds in addition to the compound of Chemical Formula 1. Examples of such additives can be exemplified by various fillers. The kind of material that can be used as the filler is not particularly limited, and all known fillers suitable for the intended use can be used. Exemplary fillers include, but are not limited to, metal materials, ceramic materials, glass, metal oxides, metal nitrides, carbon-based materials, and the like. In addition, the form of the filler is not particularly limited, and particulates, polygons including fibrous materials such as aramid fibers, glass fibers, carbon fibers or ceramic fibers, or woven fabrics, nonwoven fabrics, strings or strings, and nanoparticles formed by the materials. Or other amorphous forms. Examples of the carbon-based material may include graphite, graphene, carbon nanotubes, derivatives, isomers, and the like, such as oxides thereof. However, the components which the polymerizable composition may further include are not limited to the above, and various monomers or other known polymers that are known to be applicable to the production of so-called engineering plastics such as, for example, polyimide, polyamide or polystyrene, etc. Additives may also be included without limitation, depending on the purpose.

The present application also relates to a prepolymer formed by the reaction of the polymerizable composition, ie, the polymerizable composition comprising the compound of Formula 1.

In the present application, the term prepolymer state refers to a state in which the compound of Formula 1 and a curing agent occur to some extent in the polymerizable composition (for example, a state in which polymerization of the A or B stage stage occurs), It can mean the state which can process a composite_body | complex mentioned later, for example, showing appropriate fluidity, without reaching | attaining it.

The prepolymer may also exhibit the above-described excellent curability and low melting temperature.

The prepolymer may further comprise any known additive in addition to the above components. Examples of such an additive may include, but are not limited to, the aforementioned fillers.

The present application also relates to composites. The composite may include the phthalonitrile resin and filler described above. As described above, through the compound of Formula 1 of the present application, it is possible to achieve excellent curing properties, low melting temperature and wide process window, and thus, a so-called reinforced resin composite having excellent physical properties including various fillers ( Reinforced polymer composite can be easily formed. The composite formed as described above may include the phthalonitrile resin and the filler, and may be applied to various applications including, for example, durable materials such as automobiles, airplanes, or ships.

The type of filler is not particularly limited and may be appropriately selected in consideration of the intended use. Specific types of fillers that can be used are as described above.

The proportion of the filler is also not particularly limited and may be set in an appropriate range depending on the intended use.

The present application also relates to a precursor for preparing the composite, which precursor may comprise, for example, the polymerizable composition and the filler described above, or may comprise the prepolymer and the filler described above.

The composite can be prepared in a known manner using the precursor. For example, the composite may be formed by curing the precursor.

In one example, the precursor may be prepared by blending the polymerizable composition prepared by blending the compound of Formula 1 with a curing agent in a molten state or the prepolymer in a molten state by heating or the like. For example, the precursor prepared as described above may be molded into a desired shape and then cured to prepare the above-described composite. The polymerizable composition or prepolymer has a low melting temperature and a wide process temperature, and is excellent in curability so that molding and curing can be efficiently performed in the process.

In the above process, a method of forming a prepolymer or the like, a method of mixing the prepolymer or the like with filler, processing and curing to prepare a composite, and the like may be performed according to a known method.

The present application may also be directed to precursors of phthalocyanine dyes comprising the compounds, precursors of fluorescent brighteners or precursors of photography sensitizers, or to acid anhydrides derived from such compounds. The method of preparing the precursor or the method of preparing the acid anhydride using the compound is not particularly limited, and all known methods that can be used to prepare the precursor or acid anhydride using the phthalonitrile compound are applicable. Can be.

The present application can provide a phthalonitrile compound and its use that can be cured by itself to form a phthalonitrile resin or combined with other phthalonitrile compounds to act as a curing agent.

The phthalonitrile compound can self-curate at high speed even at low temperatures to form a phthalonitrile resin and does not create defects due to the use of existing curing agents.

In addition, the phthalonitrile compound may be combined with other compounds to be applied as a curing agent. In this case, even if the content of the compound applied as the curing agent is increased, the content of the total phthalonitrile resin does not decrease, thereby providing a resin having excellent curing degree. Can provide.

1 to 6 are NMR analysis results of the compounds prepared in Preparation Examples 1 to 6, respectively.

Hereinafter, the phthalonitrile resin and the like of the present application will be described in detail with reference to Examples and Comparative Examples, but the scope of the resin and the like is not limited to the following Examples.

1. NMR (Nuclear magnetic resonance) analysis

NMR analysis was performed according to the manufacturer's manual using Agilent's 500 MHz NMR equipment. Samples for the measurement of NMR were prepared by dissolving the compound in dimethyl sulfoxide (dSO) -d6.

2. Differential scanning calorimetry (DSC) analysis

DSC analysis was carried out in a N2 flow atmosphere with a temperature increase rate of 10 ℃ / min from 35 ℃ to 450 ℃ in the Q20 system of TA instrument.

3. Thermogravimetric Analysis (TGA) analysis

TGA analysis was performed using a TGA e850 instrument from Mettler-Toledo. In the case of the compound prepared in Preparation Example was analyzed in an N2 flow atmosphere while raising the temperature at a temperature increase rate of 10 ℃ / min from 25 ℃ to 800 ℃.

Preparation Example 1 Synthesis of Compound (PN1)

Compound (PN1) of formula A was synthesized in the following manner. 54.9 g of the compound of Formula B and 150 g of DMF (dimethyl formamide) were added to a three neck round bottom flask (RBF), followed by stirring at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula C was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the reaction was carried out while the temperature was raised to 85 ° C. while stirring, followed by cooling to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. The filtered reaction was then dried in a vacuum oven at 100 ° C. for 1 day and after removal of water and residual solvent, the compound of formula A was obtained in a yield of about 85% by weight. NMR results for the compound of Formula A are described in FIG. 1.

[Formula A]

[Formula B]

[Formula C]

Preparation Example 2 Synthesis of Compound (PN2)

Compound (PN2) of formula D was synthesized in the following manner. 32.4 g of a compound of Formula E and 130 g of DMF (dimethyl formamide) were added to a three neck round bottom flask (RBF), followed by stirring at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula C of Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. The filtered reaction was then dried in a vacuum oven at 100 ° C. for 1 day and after removal of water and residual solvent, the compound of formula D was obtained in a yield of about 80% by weight. NMR results for the compound of Formula D are shown in FIG. 2.

[Formula D]

[Formula E]

Preparation Example 3 Synthesis of Compound (PN3)

Compound (PN3) of formula F was synthesized in the following manner. 42 g of compound of Formula G and 200 g of dimethyl formamide (DMF) were added to a three neck round bottom flask (RBF), and stirred at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula C of Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. The filtered reaction was then dried in a vacuum oven at 100 ° C. for 1 day and after removal of water and residual solvent, the compound of formula F was obtained in a yield of about 82% by weight. NMR results for the compound of Formula F are shown in FIG. 3.

Formula F]

[Formula G]

Preparation Example 4 Synthesis of Compound (PN4)

Compound (PN4) of the formula H was synthesized in the following manner. 27.9 g of Compound (I) and 100 g of DMF (Dimethyl Formamide) were added to a three neck round bottom flask (RBF), followed by stirring at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula C of Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. The filtered reaction was then dried in a vacuum oven at 100 ° C. for 1 day, and after removal of water and residual solvent, the compound of formula H was obtained in a yield of about 83% by weight. NMR results for the compound of Formula H are shown in FIG. 4.

[Formula H]

[Formula I]

Preparation Example 5 Synthesis of Compound (PN5)

50.4 g of a compound of Formula K and 150 g of DMF (dimethyl formamide) were added to a three neck round bottom flask (RBF), and the mixture was stirred at room temperature to dissolve. Thereafter, 51.9 g of the compound of formula C of Preparation Example 1 was added, and 50 g of DMF was added, followed by stirring to dissolve. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. Thereafter, the filtered reaction was dried in a vacuum oven at 100 ° C. for 1 day, and after removal of water and residual solvent, the compound of formula J (PN5) was obtained in a yield of about 87% by weight. NMR results for the compound of Formula J are shown in FIG. 5.

[Formula J]

[Formula K]

Preparation Example 6 Synthesis of Compound (PN6)

The compound of formula L was synthesized in the following manner. 32.7 g of the compound of Formula M and 120 g of DMF (dimethyl formamide) were added to a three neck round bottom flask (RBF), followed by stirring at room temperature to dissolve. Subsequently, 51.9 g of the compound of formula C of Preparation Example 1 was added thereto, and 50 g of DMF was added thereto, followed by stirring to dissolve it. Subsequently, 62.2 g of potassium carbonate and 50 g of DMF were added together, and the temperature was raised to 85 ° C while stirring. After reacting for about 5 hours in the above state, the mixture was cooled to room temperature. The cooled reaction solution was poured into 0.2N aqueous hydrochloric acid solution to neutralize precipitate, and washed with water after filtering. Thereafter, the filtered reaction was dried in a vacuum oven at 100 ° C. for 1 day, and after removing water and residual solvent, a compound of formula L (PN6) was obtained in a yield of about 80% by weight. NMR results for the compound of Formula L are shown in FIG. 5.

[Formula L]

[Formula M]

Preparation Example 7 Synthesis of Compound (CA)

Compound (CA) below was obtained from TCI (Tokyo Chemical Industry Co., Ltd.) and used without further purification.

[Formula N]

Example 1.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound (PN1) of Preparation Example 1. In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material of the compound (PN1) of Preparation Example 1 for 2 hours at 240 ° C. using an IR curing oven.

Example 2.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound (PN2) of Preparation Example 2. In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured compound (PN2) of Preparation Example 2 for 2 hours at 240 ° C using an IR curing oven.

Example 3.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound of Preparation Example 3 (PN3). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material of the compound (PN3) of Preparation Example 3 for 2 hours at 240 ° C using an IR curing oven.

Example 4.

Compound (PN1) of Preparation Example 1 and Compound (PN4) of Preparation Example 4 were mixed such that about 0.2 mol of Compound (PN1) of Preparation Example 1 was present per mol of Compound (PN4) of Preparation Example 4. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

Example 5.

Compound (PN1) of Preparation Example 1 and Compound (PN5) of Preparation Example 5 were mixed so that about 0.2 mol of Compound (PN1) of Preparation Example 1 was present per mol of Compound (PN5) of Preparation Example 5. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

Example 6.

Compound (PN1) of Preparation Example 1 and Compound (PN6) of Preparation Example 6 were mixed so that about 0.2 mol of Compound (PN1) of Preparation Example 1 was present per mol of Compound (PN6) of Preparation Example 6. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

Comparative Example 1.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound (PN4) of Preparation Example 4. In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material of the compound (PN4) of Preparation Example 4 at 240 ° C. for 2 hours using an IR curing oven.

Comparative Example 2.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound (PN5) of Preparation Example 5. In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material of the compound (PN5) of Preparation Example 5 at 240 ° C. for 2 hours using an IR curing oven.

Comparative Example 3.

DSC analysis confirmed the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature) of the compound (PN6) of Preparation Example 6. In addition, the residues of Td10% and 800 ° C were confirmed through TGA analysis of the material of the compound (PN6) of Preparation Example 6 for 2 hours at 240 ° C. using an IR curing oven.

Comparative Example 4.

Compound (PN4) of Preparation Example 4 and Compound (CA) of Preparation Example 7 were mixed so that about 0.2 mol of Compound (CA) of Preparation Example 7 was present per mol of Compound (PN4) of Preparation Example 4. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

Comparative Example 5.

Compound (PN5) of Preparation Example 5 and Compound (CA) of Preparation Example 7 were mixed so that about 0.2 mol of Compound (CA) of Preparation Example 7 was present per mol of Compound (PN5) of Preparation Example 5. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

Comparative Example 6.

Compound (PN6) of Preparation Example 6 and Compound (CA) of Preparation Example 7 were mixed so that about 0.2 mol of Compound (CA) of Preparation Example 7 was present per mol of Compound (PN6) of Preparation Example 6. DSC analysis was then carried out to determine the curing start temperature (Exothermal Onset Temperature) and the maximum curing reaction temperature (Exothermal Maximum Temperature). In addition, residues at Td10% and 800 ° C were confirmed through TGA analysis of the material cured at 240 ° C for 2 hours using an IR curing oven.

The measurement results of the Examples and Comparative Examples are summarized in Table 1 below.

		Exothermal Onset Temperature	Exothermal Maximum Temperature	Td10%	Residue at 800 ℃
Example	One	255	261	472	59.6
	2	238	245	444	69
	3	166	194	369	60.2
	4	258	265	502	70
	5	260	268	473	58.6
	6	248	256	479	63.7
Comparative example	One	-	-	455	20.2
	2	-	-	422	7.3
	3	-	-	430	6.4
	4	279	283	508	69.5
	5	358	376	496	60.4
	6	301	304	478	63.4

When comparing the results of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, the curing peak was confirmed in Examples 1 to 3 even in the state of a single compound, respectively, and the curing start temperature (Exothermal Onset Temperature) and While the maximum curing reaction temperature (Exothermal Maximum Temperature) could be confirmed, in Comparative Examples 1 to 3, the curing peak could not be confirmed even when the temperature was raised to 450 ° C. In addition, in Examples 1 to 3, as a result of curing in the IR curing oven, the crosslinking reaction occurred even in a relatively short time (2 hours), and the residue at 800 ° C was 60 to 70%, showing high heat resistance. However, in Comparative Examples 1 to 3, residues at 800 ° C. were 6 to 20% even after being maintained in the curing oven.

In Examples 4 to 6, which are mixtures of the compounds of Comparative Examples 1 to 3 and the compounds of Example 1, respectively, the results of DSC confirmed that curing of the compounds of Comparative Examples 1 to 3 in which the curing reaction did not proceed alone occurred. As a result, the residue at 800 ° C. was greatly improved to 60 to 70%.

On the other hand, comparing the results of Comparative Examples 4 to 6 and Examples 4 to 6, the implementation of the compound (PN1) of Preparation Example 1 compared to Comparative Examples 4 to 6 to which the compound (CA) of Preparation Example 7 which is a known curing agent is applied In Examples 4 to 6 it was confirmed that the curing was initiated at a lower temperature, through which it can be seen that the excellent fast curing properties.

From these results, it can be seen that through the use of the compound of the present application, it is possible to secure self-curability, and to avoid void problems caused when a monomolecular curing agent or the like is introduced therethrough. In addition, it is possible to secure a higher degree of curing by preventing a decrease in the monomer ratio due to the content of the curing agent from the above properties, thereby improving the thermal and mechanical properties can be expected, lower the curing temperature, shorten the curing time Shorter process times also increase productivity.

Claims (18)

1. A compound of formula

   [Formula 1]

   

   In Formula 1, Ar ₁ and Ar ₂ are each independently an aromatic divalent radical substituted with at least one amino group or hydroxy group, and L, L ₁ and L ₂ are each independently a single bond, an alkylene group, an alkylidene group, or an oxygen group. An atom, a sulfur atom, or —S (═O) ₂ —, each of R ₁ to R ₁₀ is independently hydrogen, an alkyl group, an alkoxy group, an aryl group, or a cyano group, and at least two of R ₁ to R ₅ are cyano groups And at least two of R ₆ to R ₁₀ are cyano groups.
2. The compound according to claim 1, wherein the aromatic divalent radical in formula 1 is a divalent radical derived from an aromatic compound represented by the following formula:

   [Formula 2]

   

   Formula 2 R ₁ to R ₆ are each independently hydrogen in the alkyl group, an alkoxy group, an aryl group, a hydroxy group or are ahminogiyi, R ₁ to R at least two of the ₆ form a radical, R ₁ to R ₆ at least one of Is a hydroxyl group or an amino group.
3. The compound of claim 1, wherein the aromatic divalent radical in formula 1 is a divalent radical derived from an aromatic compound represented by the following formula:

   [Formula 3]

   

   In Formula 3 R ₁ to R ₈ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or are ahminogiyi, R ₁ to R at least two of the _eight forms a radical, R ₁ to R _8, at least one of Is a hydroxyl group or an amino group.
4. The compound according to claim 1, wherein the aromatic divalent radical in formula (1) is a divalent radical derived from an aromatic compound represented by formula (4):

   [Formula 4]

   

   In Formula 4, R ₁ to R ₁₀ are each independently hydrogen, an alkyl group, an alkoxy group, an aryl group, a hydroxy group or an amino group, at least two of R ₁ to R ₁₀ form a radical, and L is an alkylene group or an alkylidene group , An oxygen atom or a sulfur atom, and at least one of R ₁ to R ₁₀ is a hydroxy group or an amino group.
5. The compound according to any one of claims 2 to 4, wherein in Formula 2, R ₁ and R ₄ or R ₁ and R ₃ form a radical, and in Formula 3, any _one of R ₁ , R ₆ , R ₇ and R ₈ And one of R ₂ , R ₃ , R _4, and R ₅ forms a radical, and in Formula 4, any one of R ₁ to R ₅ and R ₆ to R ₁₀ form a radical.
6. The compound according to claim 2, wherein the substituent in the meta or para position is a hydroxyl group or an amino group based on the substituent forming a covalent bond with L in Formula 1 in R ₁ to R ₆ in Formula 2.
7. The compound of claim 1, wherein L in Formula 1 is a single bond, an alkylene group, an alkylene group substituted with a halogen atom, an alkylidene group, an alkylidene group substituted with a halogen atom, or —S (═O) ₂ —.
8. A compound according to claim 1, wherein L ₁ and L ₂ in formula 1 are oxygen atoms.
9. A phthalonitrile resin containing the polymerization unit derived from the compound of Claim 1.
10. A polymerizable composition comprising the compound of claim 1.
11. The polymerizable composition of claim 10, wherein the polymerizable composition does not include a compound including an amine group or a hydroxy group except for the compound of Formula 1.
12. 11. The polymerizable composition of claim 10 further comprising a phthalonitrile compound other than the compound of formula (1).
13. A prepolymer which is a reactant of the polymerizable composition of claim 10.
14. A composite comprising the phthalonitrile resin of claim 9 and a filler.
15. A precursor of a phthalocyanine dye comprising the compound of claim 1.
16. A precursor of a fluorescent brightener comprising the compound of claim 1.
17. A precursor of a photography sensitizer comprising the compound of claim 1.
18. An acid anhydride derived from the compound of claim 1.

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